Nitrile imines

ABSTRACT

Disclosed are polyfunctional nitrile imines having the formula selected from R-C identical N -N -R&#39;&#39;)x and R-N -N identical CR&#39;&#39;&#39;&#39;)x where R is an alkylene, cycloalkylene, arylene, alkylarylene, arylene-dialkylene, alkylene-diarylene or cycloalkylenedialkylene radical; R&#39;&#39; is a hydrogen, alkyl, cycloalkyl, aryl, alkaryl, or aralkyl radical; R&#39;&#39;&#39;&#39; is an alkyl, cycloalkyl, aryl, alkaryl or aralkyl radical and x is greater than 1; and their hydrogen chloride salts having the formula selected from   D R A W I N G

United States Patent I 1 Breslow [451 Aug. 27, 1974 NITRILE IMINES David S. Breslow,'Wilmington, Del.

Hercules Incorporated, Wilmington, Del.

Filed: Apr. 6, 1971 Appl. No.: 131,824

Related U.S. Application Data Continuation-impart of Ser, No. 720,430, Feb, 2, 1968, abandoned, which is a division of Ser. No. 447,887, April 13, 1965, Pat. No. 3,418,285.

Inventor:

Assignee:

U.S. Cl. 260/566 D, 260/465 E, 260/4655 Int. Cl. C07c 119/00 Field of Search 260/566 B, 566 D, 465.5,

References Cited FOREIGN PATENTS OR APPLICATIONS 793.929 9/1968 Canada 260/566 Primary ExaminerLeon Zitver Assistant E.\'aminerGerald A. Schwartz Attorney, Agent, or Firm-Marion C. Staves ABSTRACT drogen chloride salts having the formula selected from and where R, R, R" and x are as defined above which are useful cross-linking agents used in curing unsaturated polymers.

10 Claims, No Drawings NITRILE IMINES This application is a continuation-in-part of US. application Ser. No. 720,430, filed Feb. 2, 1968 now abandoned, which is in turn a division of US. application Ser. No. 447,887, filed Apr. 13, 1965, now US. Pat. No. 3,418,285.

This invention relates to new compounds useful as cross-linking agents. More particularly, the invention relates to new polyfunctional nitrile imines.

In the past, cross-linking agents used in curing unsaturated polymers suffered from certain undesirable features. For example, some prior art agents are effective in cross-linking only at high temperatures, and are adversely affected by air and moisture.

Now, in accordance with this invention, it has been found that unsaturated polymers can be cross-linked with polyfunctional nitrile imines and their hydrogen chloride salts to produce tough, solvent-resistant, cross-linked products. The instant cross-linking agents can be used at moderate temperatures, and are not adversely affected by the presence of air and moisture.

The new polyfunctional nitrile imines of this invention have the formula selected from the group Consisting of: I

RN N C-R" I wherein R is an organic radical selected from the group consisting of alkylene radicals containing 1 to 20 carbon atoms such as methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, dodecamethylene, octamethylene, octadecamethylene, eicosylene and the like; arylene radicals having 1 to 3 rings such as mand p-phenylene, biphenylene, naphthylene and anthracenediyl and the like; cycloalkylene radicals containing 3 to carbon atoms such as cyclohexylene, cyclooctylene, spiroheptylene, cyclopentylene, dicyclohexylene, cyclopropylene and cyclobutylene and the like; alkyl-arylene radicals having C -C alkyl radicals and l to 3 ring arylene radicals, such as 2,S-dimethyl-p-phenylene, 2-butyl-p-phenylene and Z-methyl-m-phenylene and the like; arylenedialkylene radicals having C ,C alkylene radicals and l to 3 ring arylene radicals such as o-, mand pxylylene and o-, mand p-phenylene-diethylene; alkylene-diarylene radicals having 1 to 3 ring arylene radicals and C -C alkylene radicals such as methylene bis(0-, mand p-phenyl), dimethylene bis(o-, mand p-phenyl) and the like; and cycloalkylene-dialkylene radicals having C1 C2U alkylene radicals and-3 to 20 carbon atoms in the cycloalkylene radical such as 12-, 1,3- or l,4-cyclohexane-dimethylene, 1,2- or l,3-cyclopentane-dimethylene and the like; R is selected from the group consisting of hydrogen, alkyl radicals containing l to 20 carbon atoms, such as methyl, butyl, nonyl, decyl, pentadecyl, eicosyl and the like; cycloalkyl radicals containing 3 to 20 carbon atoms, such as cyclopentyl, cyclooctyl, dicycloheptyl and cyclododecyl and the like; aryl radicals having 1 to 3 rings, such as phenyl, bipheny] and naphthyl radicals, alkaryl radicals having C -C alkyl groups and 1 to 3 rings in the aryl group, such as methylphenyl, octadecylnaphthyl and the like; and aralkyl radicals having C C alkyl groups and 1 to 3 rings in the aryl group, such as benzyl, naphthylhexamethylene and the like; R is the same as R except that it cannot be hydrogen; and x is an integer greater than 1. It will, of course, be obvious to those skilled in the art that R can contain functional groups or substituents, which are substantially inert to the reactions in which these compounds are used, such as halides, ethers, thioethers, and the like.

The maximum value of x in the above general formula will be dependent on the number of carbn atoms in R, since x cannot, in any case, exceed the valence of R. Preferably, x will be an integer from 2 to 10. Of particular interest in this invention are the bis(nitrile imines) illustrated by general formulae (I) and (H) above wherein x is 2. It will be obvious to those skilled in the art that the nitrile imines of formulae (1) and (II) are equivalent.

Exemplary of the new polyfunctional nitrile imines of this invention are bis(nitrile imines) such as isophthalobis(N-phenyl nitrile imine), terephthalo-bis(N-phenyl nitrile imine), isophthalo-bis(N-methyl nitrile imine), terephthalo-bis(N-methyl nitrile imine), isophthalobis(nitrile imine), terephthalo-bis(N-ethyl nitrile imine), succino-bis(N-phenyl nitrile imine), adipo-bis(N- ethylnitrile imine), Glutaro-bis(N-phenyl nitrile imwhere R, R,-R" and x are as defined above in the description of the instant nitrile imines, It will be obvious that the hydrazide chlorides of the above formulae are equivalent.

Exemplary of the hydrogen chloride salts of the instant polyfunctional nitrile imines useful in this invention are bis(hydrazide chlorides) such as isophthaloylbis(phenylhydrazide chloride), terephthaloyl-bis(- phenylhydrazide chloride), isophthaloyl-bis(methylhyand drazide chloride), isophthaloyl-bis(ethylhydrazide chloride), terephthaloyl-bis( methylhydrazide chloride), succinoyl-bis( phenylhydrazide chloride),

adipoyl-bis(methylhydrazide chloride), p-phenylene dipropionyl-bis(methylhydrazide chloride), tetramethylene dibenzoyl-bis(butylhydrazide chloride), N,N'-p-phenylene-bis(benzoyl hydrazide chloride), N,N'-m-phenylene-bis(benzoyl hydrazide chloride), glutaryl-bis(phenylhydrazide chloride), and 1,4- cyclohexane dicarboxyl-bis(phenylhydrazide chloride); and polyfunctional hydrazide chlorides containing more than two functional groups, such as trimesoyltris(phenylhydrazide chloride), trimesoyl-tris(methylhydrazide chloride), trimesoyltris(ethylhydrazide chloride), trimellitoyl-tris(phenylhydrazide chloride), trimellitoyl-tris(methylhydrazide chloride), pyromellitoyh tetrakis(butylhydrazide chloride, benezenepentacarboxyl-pentakis-(phenylhydrazide chloride), and mellitoyl-hexakis(phenylhydrazide chloride).

The polyfunctional nitrile imines of this invention are relatively unstable compounds, and the primary modes of cross-linking unsaturated polymers with these imines involves their formation in situ in a polymer mass from their closely related but more stable hydrogen chloride salts, i.e., the above-described polyfunctional hydrazide chlorides. This preparation of the nitrile imines from the hydrazide chlorides is usually accomplished by contacting the hydrazide chloride with an alkaline material. The reaction mechanism can be illustrated as follows:

The basic or alkaline material which is used in this re action can be a tertiary amine,alkali or alkaline earth metal hydroxide, alkali or alkaline earth metal salt such as carbonates or acetates or the like, or alkaline earth metal or zinc oxides.

The hydrogen chloride salts of the polyfunctional nitrile imines of this invention are themselves prepared by the reaction of phosphorus pentachloride with acyl or aroyl hydrazines. These acyl or aroyl hydrazines are prepared by the reaction of carboxylic acid chlorides with appropriately substituted hydrazines. The preparation mechanism for nitrile imines of formula (I) type can be illustrated as follows:

R(CONHNHR); XPC

The preparation mechanism for nitrile imines of Formula (ll) type can be illustrated as follows:

) xPOCl; XHCl EXAMPLE 1 A solution of parts of isophthaloyl chloride in 300 parts of chloroform is mixed with a solution of 42.5 parts of phenylhydrazine in 150 parts of chloroform over a period of 1 hour. The mixture is allowed to stand overnight, and the solid reaction product is then filtered, heated with water to remove salts, and then filtered again. The resulting product is dissolved in a mixture of dimethylformamide and water and recrystallized to yield 8.56 parts isophthaloyl-bis(phenylhydrazide) having a melting point of 269270C.

A mixture of 12.2 parts of the isophthaloyl-bis(- phenylhydrazide) so produced with parts of diethyl ether and 17.9 parts of phosphorus pentachloride is refluxed for 21.5 hours. Then 30 parts of phenol in 35 parts of diethyl ether are added, followed by 25 parts methanol. The resulting solution is filtered and the solvent evaporated until crystallization begins. The solid product is recrystallized from a mixture of acetone and water and yields 4.26 parts of isophthaloyl-bis(phenylhydrazide chloride), melting point 167.5168.5C. This product is analyzed for carbon, hydrogen and chlorine content, and the analytical results compared to the calculated amounts which should be present in C H Cl hh. The calculated amounts are C, 62.67; H, 4.21; Cl, 18.5; amounts found on analysis are: C, 62.56; H, 4.85;Cl, 17.9.

EXAMPLE 2 The procedure of Example 1 is exactly duplicated, except that 20 parts of terephthaloyl chloride is substituted for the 20 parts of isophthaloyl chloride used in Example 1. The product so produced is 2.3 parts of terephthaloyl-bis(phenylhydrazide chloride), melting point 2l4.5215C. This product is analyzed for carbon and hydrogen content, and the results are compared to amounts calculated for C H Cl N as follows:

Calculated: C, 62.67; H, 4.21 Found on analysis: C, 62.74; H, 4.53

EXAMPLE 3 A solution of 20 parts of adipoyl chloride in 300 parts of chloroform is mixed with a solution of '48 parts of phenylhydrazine in parts of chloroform over a period of 1 hour. The solid reaction product is then filtered, heated with water to remove salts and then filtered again. The resulting product is recrystallized from a mixture of dimethylformamide and water to yield 12.3 parts of adipoyl-bis(phenylhydrazide).

A mixture of 10.0 parts of the adipoyl-bis(phenylhydrazide), so produced with 100 parts of diethyl ether and 19.0 parts of phosphorus pentachloride, is refluxed for 24 hours. Then 32 parts of phenol in 35 parts of diethyl ether is added, followed by 25 parts of methanol. The resulting solution is filtered and the solvent evaporated until crystallization begins. The solid product is recrystallized from a mixture of acetone and water to yield 3.1 parts of adipoyl-bis(phenylhydrazide chloride). This product is analyzed for carbon, hydrogen and chlorine content, and the amounts found on analysis compared to amounts calculated for C H Cl N as follows:

Calculated: c, 57.91; H, 5.40; C], 19.00 Found on analysis: C, 58.10; H, 5.47; Cl, 18.90

EXAMPLE 4 tered, heated with water to remove salts, and then filtered again. The resulting product is dissolved in a mixture of dimethylformamide and water and recrystallized to yield 10.3 parts of trimesoyl-tris(phenylhydrazide).

A mixture of 10.0 parts of the trimesoyl-tris(phenylhydrazide) so produced, with 150 parts of diethyl ether and 15.0 parts of phosphorus pentachloride, is refluxed for 24 hours. Then 25 parts of phenol in 50 parts of diethyl ether is added, followed by 20 parts of methanol. The resulting solution is filtered and the solvent evaporated until crystallization begins. The solid product is recrystallized from a mixture of acetone and water to yield 2.7 parts of trimesoyl-tris(phenylhydrazide chloride). Analysis of this product shows the following:

Calculated amounts for C H Cl N C, 60.51; H, 3.95; Cl, 19.85

Amounts found on analysis: C, 60.39; H, 3.90; Cl, 20.01

EXAMPLE 5 A mixture of 10 parts of benzoyl chloride in 100 parts of chloroform, 120 parts of water and 3.0 parts of sodium hydroxide is mixed with a solution of 4.92 parts of p-phenylene bis(hydrazine) in 50 parts of chloroform over a period of 1 hour. The solid reaction product is then filtered, heated with water, and then filtered again. The resulting product is recrystallized from a mixture of dimethylformamide and water to yield 6.4 parts of N.N'-p-phenylene bis( benzoyl hydrazide).

A mixture of 10.0 parts of the bis(benzoyl hydrazide) with 100 parts of diethyl ether and parts of phosphorus pentachloride is refluxed for 24 hours. Then 25 parts of phenol in 50 parts of diethyl ether is added, followed by 21 parts of methanol. The resulting solution is filtered and the solvent evaporated until crystallization begins. The solid product is recrystallized from a mixture of acetone and water to yield 4.3 parts of N,N- v

p-phenylene bis(benzoyl hydrazide chloride). This product was analyzed for carbon, hydrogen and chlorine content as follows:

Amounts calculated for C l-l Cl N C, 62.67; H, 4.21; Cl, 18.50

Amounts found on analysis: C, 62.81; H, 4.13; Cl, 18.62

EXAMPLE 6 A solution of 10 parts of 1,4-cyelohexanedicarbonyl chloride in 200 parts of chloroform is mixed with a solution of 21 parts of phenylhydrazine in 75 parts of chloroform. The solid'product is collected by filtration ing material is then recrystallized from dimethylformamide and water to yield 5.9 parts of 1,4-' cyclohexanedicarbonyl-bis(phenyldrazide).

A mixture of 5 parts of the 1,4-

and washed with hot water to remove salts. The result- Analysis Found Calculated for C H Cl- N V C 62.1 61.8 H 5.88 5.66 C1 17.8 18.2

EXAMPLE 7 A solution of 15 parts of 4,4'-methylenedibenzoyl chloride in 285 parts of chloroform is added to a solution of 22.2 parts of phenylhydrazine in 125 parts of chloroform. After stirring overnight, the solid product is collected by filtration and washed with hot water to remove salts. The resulting material is then recrystallized from dimethylfonnamide and water to give 9.1 parts of the 4,4'-methylenedibenzoyl-bis(phenylhydrazide).

A mixture of the above bis(phenylhydrazide) in parts of diethyl ether and 7. 15 parts of phosphorus pen- I Analysis Found Calculated for C H Cl N C 68.9 68.5 H 4.90 4.65 CI 14.6 15.0

EXAMPLE 8 A mixture of 6.3 parts of benzoyl chloride in 70 parts of chloroform, parts of water and 2.0 parts of sodium hydroxide is mixed with a solution of 4.5 parts of 2-methyl-l ,4-napthylene-bis( hydrazine) in 100 parts of chloroform. After stirring for 18 hours, the reaction mixture is filtered and the solid washed with hot water to remove salts. The resulting product is recrystallized from a mixture of dimethylformamide and water to yield 5.8 parts of 2-methyl-N-N'-l,4-naphthy1ene-' bis(benzoyl hydrazide).

A mixture of 5.0 parts of the above bis(benzoyl hydrazide) with 60 parts of diethyl ether and 5.9 parts of phosphorus pentachloride is refluxed for 24 hours. A solution of 10 parts of phenol in 25 parts of ether is then added, followed by 10 parts of methyl alcohol. The reaction mixture is concentrated until crystallization begins. The product is collected by filtration and recrystallized from acetone-water to yield 1.8 parts of 2-methyl-N,N'- 1 ,4-naphthylene-bis(benzoyl hydrazide chloride) having the formula; u

The product is analyzed for carbon, hydrogen and chlorine as follows:

A mixture of 10.3 parts of benzoyl chloride in 75 parts of chloroform, 150 parts of water and 3.1 parts of sodium hydroxide is mixed with 8.3 parts of 4,4- methylene-bis(phenylhydrazide) in 150 parts of chloroform. After stirring for 4 hours the reaction product is filtered and washed with hot water. A recrystallization from dimethylformamide and water yields 10.8 parts of 4,4'-methylene-bis(N-benzoylphenylhydrazide).

A mixture of 8.5 parts of the above bis(N-benzoylphenylhydrazide) with 80 parts of ether and 9.4 parts of phosphorus pentachloride is refluxed for 19 hours. A solution of 20 parts of phenol in 50 parts of other is added, followed by 15 parts of methyl alcohol. The reaction mixture is then filtered and the clear solution concentrated until crystallization begins. The solid product is collected by filtration and recrystallized from acetone-water to yield 3.2 parts of 4,4- methylene-bis(N-benzoylphenylhydrazide chloride) having the formula:

The product is analyzed for carbon, hydrogen and chlorine as follows:

Analysis Found Calculated for C H- CI PL C 28.8 68.4 H 4.75 4.65 CI l4.5 15.0

examples, as will be readily apparent to those skilled in the art.

As pointed out above, the polyfunctional hydrazide chlorides so produced are treated with a basic or alkaline material to produce the polyfunctional nitrile imines of this invention. Since the preferred formation of these nitrile imine cross-linking agents is in situ in the polymer mass, their preparation from their hydrogen chloride salts will be specifically illustrated along with the production of the cross-linked polymers in the examples set forth hereinafter.

The nitrile imines of this invention can also be prepared from polyfunctional tetrazoles, which on heating yield nitrogen and a nitrile imine, as shown by the following reaction mechanism:

vention include tetrarnethylene bis-S-(tetrazole), p-

phenylene bis-S-(tetrazole), hexamethylene bis-5- (tetrazole), and p-phenylene bis-5-( 2-phenyltetrazole).

Generally, any type of unsaturated polymer, containing ethylenic unsaturation wherein there is at least one hydrogen radical attached to at least one of the carbon atoms of the double bond, can be cross-linked with the above-described polyfunctional nitrile imines and their hydrogen chloride salts, as described in parent applicationSer. No. 447,887, now US. Pat. No. 3,418,285. Among the polymers which can be cross-linked in this manner are polybutadiene-l,2; polybutadiene-l,4; styrene-butadiene copolymers; butyl rubber (polyisobutyleneisoprene copolymers); natural rubber; polyester resins, such as, for example, maleate containing polyesters and polyacrylate esters; butadiene-acrylonitrile copolymers; ethylene-- propylenedicyclopentadiene terpolymers; polychlo roprene; polyisoprene, alkyd resins such as, for example, tall oil alkyd resins; polyether copolymers and terpolymers containing at least one unsaturated epoxide constituent, such as, for example, propylene oxideallyl glycidyl ether copolymer and ethylene oxide-epichlorohydrinallyl glycidyl ether terpolymers; and other similar hydrocarbon or non-hydrocarbon unsaturated polymers. ln addition to the above olefinically unsaturated polymers, polymers containing acetylenic unsaturation can be similarly cross-linked. Mixtures or blends of two or more of the above types of polymers may also be cross-linked.

The cross-linking is carried out by contacting the unsaturated polymer and a minor amount of the polyfunctional nitrile imine cross-linking agent for a time sufficient for the desired degree of cross-linking to occur. This uniform contacting is preferably achieved by uniformly mixing the polymer and the hydrogen chloride salt of the polyfunctional nitrile imine, and treating that mixture with an alkaline material, thereby generating the nitrile imine in situ in the polymer mass.

Alternatively, a polyfunctional tetrazole of the type described above can be uniformly incorporated in the polymer mass. When this tetrazolepolymer mixture is heated to a temperature above about 100C., the polyfunctional tetrazole will break down, generating its corresponding polyfunctional nitrile imine and nitrogen gas, and the polyfunctional nitrile imine will thus uniformly contact the surrounding polymer mass, thereby initiating the cross-linking reaction.

The amount of polyfunctional nitrile imine crosslinker brought into contact with the unsaturated polymer will depend on the amount of cross-linking desired. While the polymer can be effectively contacted with from about 0.01 percent to about 50 percent by weight of the polymer of the hydrogen chloride salt of the polyfunctional nitrile imine, amounts between about 0.1 percent and 10 percent by weight of the polymer of that salt are preferred. Like amounts of polyfunctional tetrazoleprecursor can also be used.

The rate of cross-linking will depend on the temperatures at which the unsaturated polymer and the polyfunctional nitrile imine are contacted. If the preferred procedure of adding the hydrogen chloride salt of the nitrile imine to the polymer is followed, very moderate temperatures can be used. Even contacting the polymer and cross-linking agent at room temperature produces highly satisfactory results. When using this method, temperatures between about 0200C. are generally used, with temperatures between about -l00C. being preferred. lf the altemative method, using the tetrazole precursors, is used, temperatures between about lO0-300C. must be used, with 150250C. being preferred.

The uniform mixing of the unsaturated polymer with the hydrogen chloride salt of the instant nitrile imine or with the tetrazole precursor of the nitrile iminecan be carried out by milling these ingredients on a conventional rubber mill, by dissolving the hydrogen chloride salt or the tetrazoleprecursor in a solvent solution of the polymer, or by any of other numerous methods, which will be readily apparent to those skilled in the art. This uniform contacting will result in the nitrile imine cross-linking agent being uniformly distributed throughout the polymer mass upon its in situ generation, so that uniform cross-linking can be achieved.

Additional ingredients can be incorporated in the polymer-salt or polymer-precursorblend, if desired. Common rubber additives such as, for example, extenders. fillers. pigments, plasticizers and stabilizers, can be included. In many cases, however, it will be more desirable to omit such additives and add only the hydrogen chloride salt of the polyfunctional nitrile imine or the tetrazole precursor of the polyfunctional nitrile imine to the unsaturated polymer.

The resulting cross-linked polymers are hard, tough rubbers, which are substantially insoluble in water and hydrocarbon solvents. They exhibit improved tensile properties over their uncured counterparts. These polymers are useful in various rubber applications, such as, for example, as protective and decorative coatings for various substrates including wood, metals,

paper and plastics; as ingredients of tires for motor vehicles, tubing, pipe and other rubber articles; and the like.

The preparation of the instant cross-linked polymers will be further illustrated by the following specific examples. All parts and percentages referred to therein are by weight unless otherwise specifically indicated. The molecular weight of the polymers used in these examples is indicated by their Reduced Specific Viscosity. By the term Reduced Specific Viscosity (RSV) is meant the 'nsp/c determined on a 0. 1 percent solution (0. 1 gram of the polymer per ml. of solution) of the polymer in a given solvent at the specified temperature.

EXAMPLE 10 In this example, 0.05 part of the isophthaloyl-bis(- phenylhydrazide chloride) prepared in Example 1 is uniformly mixed with a solution of 0.05 part of a maleateisophthalatepropylene glycol polyester (Oronite Resin CR 19583, produced by the Oronite Chemical Co.), [RSV 0.09 in benzene at 25C.] in 4 parts of acetone, and this mixture is evaporated to dryness at room temperature. The solid residue is treated with vapors of triethylamine for 1.5 hours at 25C. The resulting product is a hard, tough material, substantially insoluble in acetone.

EXAMPLE 1 1 In this example, 0.05 part of the isophthaloyl-bis(- phenylhydrazide chloride) prepared in Example 1 is uniformly mixed with a solution of 1.0 part of a propylene oxideallyl glycidyl ether copolymer (10 percent by weight of copolymer of allyl glycidyl ether) [RSV 5.2 in benzene at 25C.] in about 20 parts of a benzeneacetone solvent, and the resulting mixture is evaporated to dryness at room temperature. The solid rubber residue is treated with vapors of triethylamine for 5.0 hours at 30C. The resulting product is a hard, tough rubber, substantially insoluble in chloroform.

The above procedure is exactly duplicated, except that no hydrazide chloride is added to the polymer solution. The rubber product so produced is completely soluble in chloroform.

EXAMPLE 12 ln this example, 0.05 part of the terephthaloyl-bis(- EXAMPLE 13 In this example, 0.01 part of the adipoyl-bis(phenylhydrazide chloride) prepared in Example 3 is mixed with a solution of 1.0 part of l,2-poly(butadiene) (RSV 3.2 in benzene at 25C.) in 20 parts of benzene, and this mixture is evaporated to dryness at room temperature. The residue is treated with vapors of triethylamine for 3.0 hours at 60C. The resulting product is substantially insoluble in toluene.

FXAMPIF. M

In this example, 0.005 part of the trimesoyl-tris(- phenylhydrazide chloride) prepared in Example 4, is mixed with a solution of 1.0 part of styrene-butadiene rubber (25 weight percent styrene, RSV 2.0 in benezene at 25C.) in 30 parts of benzene and the resulting mixture is evaporated to dryness at room temperature. The solid rubber residue is treated with vapors of triethylamine for 8 hours at 60C. The product is substan tially insoluble in benzene.

EXAMPLE 15 l. A compound selected from the group consisting of wherein R is a radical selected from the group consisting of methylene, dimethylene, trimethylene, tetramethylene. pentamethylene, hexamethylene, octamethylene. dodecamethylene octadecamethylene, ophenylene, m-phenylene, p-phenylene, biphenylene, naphthylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, o-xylylene, m-xylylene, pxylylene, o-phenylene-diethylene, m-phenylenediethylene, p-phenylene-diethylene, methylene bis(ophenyl), methylene bis(m-phenyl), methylene bis(p phenyl), dimethylene bis(o-phenyl), dimethylene bis(m-phenyl), dimethylene bis(p-phenyl), 1,2- cyclohexane-dimethylene, l ,3-cyclohexanedimethylene, l,4-cycloheXane-dimethylene, 1,2-cyclopentane-dimethylene and 1,3-cyclopentanedimethylene; R is a radical selected from the group consisting of hydrogen, C -C alkyl, C -,-C cycloalkyl, aryl having 1 to 3 rings, alkaryl having C C alkyl groups and l to 3 ring and aralkyl having 1 to 3 rings and C -C alkyl groups; R" is a radical selected from the group consisting of C -C alkyl, C -C cycloalkyl, aryl having 1 to 3 rings, alkaryl having C -C alkyl groups and l to 3 rings and aralkyl having 1 to 3 rings and C -C alkyl; and is an integer from 2 to 10. 2. The compound of claim 1 having the formula 3. The compound of claim 2 wherein R is selected from the group consisting of o-phenylene, mphenylene, p-phenylene, biphenylene and naphthylene and R is an aryl radical having 1 to 3 rings.

4. A compound having the formula wherein R is a radical selected from the group consisting of o-phcnylcnc, Illpllcllyllw, p-phenylene, biphenylene and naphthylene and R is an aryl radical having 1 to 3 rings, and x is an integer from 2 to 10.

5. A compound having the formula wherein R is a radical selected from the group consisting of o-phenylene, m-phenylene, p-phenylene, biphenylene and naphthylene and R" is an aryl radical having 1 to 3 rings, and x is an integer from 2 to 10.

6. l,4-Cyclohexanedicarbonyl-bis(phenylhydrazide chloride).

7. lsophthaloyl-bis(phenylhydrazide chloride) having the formula 8. Terephthaloyl-bis(phenylhydrazide chloride) having the formula 9. Trimesoyl-tris(phenylhydrazide chloride) having the formula 10. N,N-p-phenylene bis(benzoyl hydrazide chloride) having the formula 22 53 --UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIQN Patent No. 3,832,399 Dated August 27, 1974 Inventofls) David S. Breslow It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column l, first 2 formulas of printed patent reads should read Column 5 line 56 of printed patent;

(phenyldrazide) should read (phenylhydrazide) Signed and sealed this 4th day of February 1975.

(SEAL) Attest:

McCOY {4. GIBSON JR. C. MARSHALL DANN Attestlng 0ff1cer Commissioner of Patents 

2. The compound of claim 1 having the formula
 3. The compound of claim 2 wherein R is selected from the group consisting of o-phenylene, m-phenylene, p-phenylene, biphenylene and naphthylene and R'' is an aryl radical having 1 to 3 rings.
 4. A compound having the formula
 5. A compound having the formula
 6. 1,4-Cyclohexanedicarbonyl-bis(phenylhydrazide chloride).
 7. Isophthaloyl-bis(phenylhydrazide chloride) having the formula
 8. Terephthaloyl-bis(phenylhydrazide chloride) having the formula
 9. Trimesoyl-tris(phenylhydrazide chloride) having the formula
 10. N,N''-p-phenylene bis(benzoyl hydrazide chloride) having the formula 